Real-Space Observation of Ligand Hole State in Cubic Perovskite SrFeO3.

An anomalously high valence state sometimes shows up in transition-metal oxide compounds. In such systems, holes tend to occupy mainly the ligand p orbitals, giving rise to interesting physical properties such as superconductivity in cuprates and rich magnetic phases in ferrates. However, no one has ever observed the distribution of ligand holes in real space. Here, a successful observation of the spatial distribution of valence electrons in cubic perovskite SrFeO3 by high-energy X-ray diffraction experiments and precise electron density analysis using a core differential Fourier synthesis method is reported. A real-space picture of ligand holes formed by the orbital hybridization of Fe 3d and O 2p is revealed. The anomalous valence state in Fe is attributed to the considerable contribution of the ligand hole, which is related to the metallic nature and the absence of Jahn-Teller distortions in this system.

Double dome structure of the Bose-Einstein condensation in diluted S = 3/2 quantum magnets.

Bose-Einstein condensation (BEC) in quantum magnets, where bosonic spin excitations condense into ordered ground states, is a realization of BEC in a thermodynamic limit. Although previous magnetic BEC studies have focused on magnets with small spins of S ≤ 1, larger spin systems potentially possess richer physics because of the multiple excitations on a single site level. Here, we show the evolution of the magnetic phase diagram of S = 3/2 quantum magnet Ba2CoGe2O7 when the averaged interaction J is controlled by a dilution of magnetic sites. By partial substitution of Co with nonmagnetic Zn, the magnetic order dome transforms into a double dome structure, which can be explained by three kinds of magnetic BECs with distinct excitations. Furthermore, we show the importance of the randomness effects induced by the quenched disorder: we discuss the relevance of geometrical percolation and Bose/Mott glass physics near the BEC quantum critical point.

Spin-Lattice and Magnetoelectric Couplings Enhanced by Orbital Degrees of Freedom in Polar Multiferroic Semiconductors.

Orbital degrees of freedom mediating an interaction between spin and lattice were predicted to raise strong magnetoelectric effect, i.e., to realize an efficient coupling between magnetic and ferroelectric orders. However, the effect of orbital fluctuations has been considered only in a few magnetoelectric materials, as orbital-degeneracy driven Jahn-Teller effect rarely couples to polarization. Here, we explore the spin-lattice coupling in multiferroic Swedenborgites with mixed valence and Jahn-Teller active transition metal ions on a stacked triangular and Kagome lattice using infrared and dielectric spectroscopy. On one hand, in CaBaM_{4}O_{7} (M=Co, Fe), we observe a strong magnetic-order-induced shift in the phonon frequencies and a corresponding large change in the dielectric response. Remarkably, as an unusual manifestation of the spin-phonon coupling, the spin fluctuations reduce the phonon lifetime by one order of magnitude at the magnetic phase transitions. On the other hand, lattice vibrations, dielectric response, and electric polarization show no variation at the Néel temperature of CaBaFe_{2}Co_{2}O_{7}, which is built up by orbital singlet ions. Our results provide a showcase for orbital degrees of freedom enhanced magnetoelectric coupling via the example of Swedenborgites.

Magnetoelectric transfer of a domain pattern.

The utility of ferroic materials is determined by the formation of domains and their poling behavior under externally applied fields. For multiferroics, which exhibit several types of ferroic order at once, it is also relevant how the domains of the coexisting ferroic states couple and what kind of functionality this might involve. In this work, we demonstrate the reversible transfer of a domain pattern between magnetization and electric-polarization space in the multiferroic Dy0.7Tb0.3FeO3. A magnetic field transfers a ferromagnetic domain pattern into an identical ferroelectric domain pattern while erasing it at its magnetic origin. Reverse transfer completes the cycle. To assess the generality of our experiment, we elaborate on its conceptual origin and aspects of application.

Magnetochiral Dichroism in a Collinear Antiferromagnet with No Magnetization.

We show the directional dichroism in a collinear antiferromagnet MnTiO_{3}. The dichroism between two distinctive antiferromagnetic states with opposite signs of staggered magnetic moments can be regarded as magnetochiral dichroism in the absence of external fields. Electric-field reversal of antiferromagnetic domain causes a change in the absorption intensity of unpolarized light around 2.15 eV. The difference in optical absorption between two antiferromagnetic states is reversed for the light propagating in the opposite direction. The absorption coefficient displays a hysteretic behavior for a cycle of sweeping the external electric or magnetic field.

Disordered skyrmion phase stabilized by magnetic frustration in a chiral magnet.

Magnetic skyrmions are vortex-like topological spin textures often observed to form a triangular-lattice skyrmion crystal in structurally chiral magnets with the Dzyaloshinskii-Moriya interaction. Recently, ß-Mn structure-type Co-Zn-Mn alloys were identified as a new class of chiral magnet to host such skyrmion crystal phases, while ß-Mn itself is known as hosting an elemental geometrically frustrated spin liquid. We report the intermediate composition system Co7Zn7Mn6 to be a unique host of two disconnected, thermal-equilibrium topological skyrmion phases; one is a conventional skyrmion crystal phase stabilized by thermal fluctuations and restricted to exist just below the magnetic transition temperature Tc, and the other is a novel three-dimensionally disordered skyrmion phase that is stable well below Tc. The stability of this new disordered skyrmion phase is due to a cooperative interplay between the chiral magnetism with the Dzyaloshinskii-Moriya interaction and the frustrated magnetism inherent to ß-Mn.

Identification of Antiferromagnetic Domains Via the Optical Magnetoelectric Effect.

The ultimate goal of multiferroic research is the development of a new-generation nonvolatile memory devices, where magnetic bits are controlled via electric fields with low energy consumption. Here, we demonstrate the optical identification of magnetoelectric (ME) antiferromagnetic (AFM) domains in the LiCoPO_{4} exploiting the strong absorption difference between the domains. This unusual contrast, also present in zero magnetic field, is attributed to the dynamic ME effect of the spin-wave excitations, as confirmed by our microscopic model, which also captures the characteristics of the observed static ME effect. The control and the optical readout of AFM/ME domains, demonstrated here, will likely promote the development of ME and spintronic devices based on AFM insulators.

Rapid on-site monitoring of Legionella pneumophila in cooling tower water using a portable microfluidic system.

Legionnaires' disease, predominantly caused by the bacterium Legionella pneumophila, has increased in prevalence worldwide. The most common mode of transmission of Legionella is inhalation of contaminated aerosols, such as those generated by cooling towers. Simple, rapid and accurate methods to enumerate L. pneumophila are required to prevent the spread of this organism. Here, we applied a microfluidic device for on-chip fluorescent staining and semi-automated counting of L. pneumophila in cooling tower water. We also constructed a portable system for rapid on-site monitoring and used it to enumerate target bacterial cells rapidly flowing in the microchannel. A fluorescently-labelled polyclonal antibody was used for the selective detection of L. pneumophila serogroup 1 in the samples. The counts of L. pneumophila in cooling tower water obtained using the system and fluorescence microscopy were similar. The detection limit of the system was 104 cells/ml, but lower numbers of L. pneumophila cells (101 to 103 cells/ml) could be detected following concentration of 0.5-3 L of the water sample by filtration. Our technique is rapid to perform (1.5 h), semi-automated (on-chip staining and counting), and portable for on-site measurement, and it may therefore be effective in the initial screening of Legionella contamination in freshwater.

Current-Induced Nucleation and Annihilation of Magnetic Skyrmions at Room Temperature in a Chiral Magnet.

A magnetic skyrmion is a nanometer-scale magnetic vortex carrying an integer topological charge. Skyrmions show a promise for potential application in low-power-consumption and high-density memory devices. To promote their use in applications, it is attempted to control the existence of skyrmions using low electric currents at room temperature (RT). This study presents real-space observations for the current-induced formation and annihilation of a skyrmion lattice (SkL) as well as isolated skyrmions in a microdevice composed of a thin chiral magnet Co8 Zn9 Mn3 with a Curie temperature, TC ≈ 325 K, above RT. It is found that the critical current for the manipulation of Bloch-type skyrmions is on the order of 108 A m-2 , approximately three orders of magnitude lower than that needed for the creation and drive of ferromagnetic (FM) domain walls in thin FM films. The in situ real-space imaging also demonstrates the dynamical topological transition from a helical or conical structure to a SkL induced by the flow of DC current, thus paving the way for the electrical control of magnetic skyrmions.

Deformation of Topologically-Protected Supercooled Skyrmions in a Thin Plate of Chiral Magnet Co8Zn8Mn4.

Magnetic skyrmions in Co8Zn8Mn4 thin plates are observed to deform in a metastable state prepared in a magnetic-field-cooling process by way of the thermal-equilibrium skyrmion phase. In cooling, the disk-shape skyrmions change to bar- or L-shaped elongated form, whereas the skyrmion density is nearly conserved. The deformation of the skyrmions in the supercooled metastable phase is observed irrespective of the crystallographic orientation of the thin plate, whereas the elongation direction nearly aligns along the magnetic easy axis. It is proposed that the deformation should be induced by a large increase in magnetic modulation wavenumber when decreasing the temperature, whereas the topological protection of the skyrmions keeps the averaged skyrmion density constant.

Variation of Topology in Magnetic Bubbles in a Colossal Magnetoresistive Manganite.

The emergence of zero-bias bubbles (≈100 nm in diameter) with various Bloch lines and their triangular lattice is revealed in a colossal magnetoresistive material, La1-x Srx MnO3 , by means of Lorentz transmission electron microscopy (LTEM). The magnetization dynamics, and accompanying changes of the topological number of bubbles via the field-driven motion of the Bloch lines, are demonstrated by in situ LTEM observations.

Highly efficient gene transfer using a retroviral vector into murine T cells for preclinical chimeric antigen receptor-expressing T cell therapy.

Adoptive immunotherapy using chimeric antigen receptor-expressing T (CAR-T) cells has attracted attention as an efficacious strategy for cancer treatment. To prove the efficacy and safety of CAR-T cell therapy, the elucidation of immunological mechanisms underlying it in mice is required. Although a retroviral vector (Rv) is mainly used for the introduction of CAR to murine T cells, gene transduction efficiency is generally less than 50%. The low transduction efficiency causes poor precision in the functional analysis of CAR-T cells. We attempted to improve the Rv gene transduction protocol to more efficiently generate functional CAR-T cells by optimizing the period of pre-cultivation and antibody stimulation. In the improved protocol, gene transduction efficiency to murine T cells was more than 90%. In addition, almost all of the prepared murine T cells expressed CAR after puromycin selection. These CAR-T cells had antigen-specific cytotoxic activity and secreted multiple cytokines by antigen stimulation. We believe that our optimized gene transduction protocol for murine T cells contributes to the advancement of T cell biology and development of immunotherapy using genetically engineered T cells.

Piezomagnetoelectric Effect of Spin Origin in Dysprosium Orthoferrite.

The piezomagnetoelectric effect, namely, the simultaneous induction of both the ferromagnetic moment and electric polarization by an application of uniaxial stress, was demonstrated in the nonferroelectric antiferromagnetic ground state of DyFeO(3). The induced electric polarization and ferromagnetic moment are coupled with each other, and monotonically increase with increasing uniaxial stress. The present work provides a new guiding principle for designing multiferroics where its magnetic symmetry is broken by external uniaxial stress.

Charge-order domain walls with enhanced conductivity in a layered manganite.

Interfaces and boundaries in condensed-matter systems often have electronic properties distinct from the bulk material and thus have become a topic of both fundamental scientific interest and technological importance. Here we identify, using microwave impedance microscopy, enhanced conductivity of charge-order domain walls in the layered manganite Pr(Sr0.1Ca0.9)2Mn2O7. We obtain a complete mesoscopic map of surface topography, crystalline orientation and electronic phase, and visualize the thermal phase transition between two charge-ordered phases. In both phases, charge-order domains occur with domain walls showing enhanced conductivity likely due to local lifting of the charge order. Finite element analysis shows that the resolved domain walls can be as narrow as few nanometres. The domain walls are stabilized by structural twins and have a strong history dependence, suggesting that they may be manipulated to create novel devices.

Uniaxial-stress control of spin-driven ferroelectricity in multiferroic Ba(2)CoGe(2)O(7).

We have demonstrated that spin-driven ferroelectricity in a tetragonal multiferroic Ba(2)CoGe(2)O(7) is controlled by applying uniaxial stress. We found that the application of compressive stress along the [110] direction leads to a 45° or 135° rotation of the sublattice magnetization of the staggered antiferromagnetic order in this system. This allows the spontaneous electric polarization to appear along the c axis. The present study suggests that an application of anisotropic stress, which is the simplest way to control symmetry of matter, can induce a variety of cross-correlated phenomena in spin-driven multiferroics.

Magnetic stripes and skyrmions with helicity reversals.

It was recently realized that topological spin textures do not merely have mathematical beauty but can also give rise to unique functionalities of magnetic materials. An example is the skyrmion--a nano-sized bundle of noncoplanar spins--that by virtue of its nontrivial topology acts as a flux of magnetic field on spin-polarized electrons. Lorentz transmission electron microscopy recently emerged as a powerful tool for direct visualization of skyrmions in noncentrosymmetric helimagnets. Topologically, skyrmions are equivalent to magnetic bubbles (cylindrical domains) in ferromagnetic thin films, which were extensively explored in the 1970s for data storage applications. In this study we use Lorentz microscopy to image magnetic domain patterns in the prototypical magnetic oxide-M-type hexaferrite with a hint of scandium. Surprisingly, we find that the magnetic bubbles and stripes in the hexaferrite have a much more complex structure than the skyrmions and spirals in helimagnets, which we associate with the new degree of freedom--helicity (or vector spin chirality) describing the direction of spin rotation across the domain walls. We observe numerous random reversals of helicity in the stripe domain state. Random helicity of cylindrical domain walls coexists with the positional order of magnetic bubbles in a triangular lattice. Most unexpectedly, we observe regular helicity reversals inside skyrmions with an unusual multiple-ring structure.

High-pressure hydrothermal crystal growth and multiferroic properties of a perovskite YMnO3.

Orthorhombic perovskites RMnO(3) are representative of spin-driven ferroelectrics. When the radius of the rare-earth ion R is smaller than that of Dy, for instance in YMnO(3), the orthorhombic phase becomes metastable at ambient pressure, which impedes the crystal growth; thus, the detailed magnetic and multiferroic properties of the metastable phase have not been characterized. In this work, we successfully obtained single crystals of orthorhombic YMnO(3) using quasi-hydrothermal conditions under a high pressure of 5.5 GPa. Magnetic and dielectric measurements under magnetic fields revealed that the magnetic ground state is the commensurate E-type antiferromagnetic, while a cycloidal spin phase likely coexists in the intermediate temperature range, which enhances the magnetoelectric response to external fields.

Above-room-temperature ferroelectricity in a single-component molecular crystal.

Ferroelectrics are electro-active materials that can store and switch their polarity (ferroelectricity), sense temperature changes (pyroelectricity), interchange electric and mechanical functions (piezoelectricity), and manipulate light (through optical nonlinearities and the electro-optic effect): all of these functions have practical applications. Topological switching of pi-conjugation in organic molecules, such as the keto-enol transformation, has long been anticipated as a means of realizing these phenomena in molecular assemblies and crystals. Croconic acid, an ingredient of black dyes, was recently found to have a hydrogen-bonded polar structure in a crystalline state. Here we demonstrate that application of an electric field can coherently align the molecular polarities in crystalline croconic acid, as indicated by an increase of optical second harmonic generation, and produce a well-defined polarization hysteresis at room temperature. To make this simple pentagonal molecule ferroelectric, we switched the pi-bond topology using synchronized proton transfer instead of rigid-body rotation. Of the organic ferroelectrics, this molecular crystal exhibits the highest spontaneous polarization ( approximately 20 muC cm(-2)) in spite of its small molecular size, which is in accord with first-principles electronic-structure calculations. Such high polarization, which persists up to 400 K, may find application in active capacitor and nonlinear optics elements in future organic electronics.

Composite domain walls in a multiferroic perovskite ferrite.

Controlling ferromagnetism by an external electric field has been a great challenge in materials physics, for example towards the development of low-power-consumption spintronics devices. To achieve an efficient mutual control of electricity and magnetism, the use of multiferroics--materials that show both ferroelectric and ferromagnetic/antiferromagnetic order--is one of the most promising approaches. Here, we show that GdFeO(3), one of the most orthodox perovskite oxides, is not only a weak ferromagnet but also possesses a ferroelectric ground state, in which the ferroelectric polarization is generated by the striction through the exchange interaction between the Gd and Fe spins. Furthermore, in this compound, ferroelectric polarization and magnetization are successfully controlled by magnetic and electric fields, respectively. This unprecedented mutual controllability of electricity and magnetism is attributed to the unique feature of composite domain wall clamping of the respective domain walls for electric and magnetic orders. This domain wall feature generally determines the efficiency of the mutual controllability and thus could have an important role towards the application of multiferroics to practical devices.

Proton dynamics and room-temperature ferroelectricity in anilate salts with a proton sponge.

Ferroelectricity as well as characteristic proton-transfer dynamics are achieved by combining a 2,3,5,6-tetra(2'-pyridyl)pyrazine (TPPZ) molecule with anilic acids (H2xa). Dielectric measurements revealed phase transitions at T(c) = 334 and 172 K for bromanilate (Hba(-)) and chloranilate (Hca(-)) salts, respectively. The room-temperature ferroelectricity of the (H2-TPPZ)(Hba)2 crystal is evidenced by the slow polarization reversal with modest pyroelectricity. In accord with the observed large deuteration effect, synchrotron X-ray diffraction studies disclosed proton dynamics in an intramolecular N...H(+)...N bond of the H2-TPPZ(2+) dication and in an O-H...O(-) hydrogen-bonded cyclic dimer of the ortho-quinoid Hxa(-) anions. The disordered (Hxa(-))2 dimer in two-fold orientation manifests its double-proton transfer process above T(c), whereas these protons are ordered in the ferroelectric phase. The H2-TPPZ(2+) dication acts as a proton sponge by forming two intramolecular N...H(+)...N hydrogen bridges between the pyridyl units with a very short N...N distance. The dication in the paraelectric state adopts a nonpolar geometry due to the delocalization of the protons over two sites in the respective N...H(+)...N bonds. Below T(c), only one of the two protons gets localized, and the resultant acentric H2-TPPZ(2+) ion generates the dipole moment responsible for the ferroelectricity.